Tertiary amine composition and method for making the composition

ABSTRACT

A composition and method for producing a tertiary amine is disclosed. The tertiary amine is contacted with an inert gas. The inert gas is nitrogen or more preferably argon. The amine composition is useful in producing polyurethane foam with lower levels of chemical emissions particularly lower emissions of toxic chemicals.

CROSS-REFERENCE TO RELATED APPLICATIONS

This Application is a divisional application of U.S. application Ser.No. 13/633,423, filed Oct. 2, 2012, now U.S. Pat. No. 9,273,175. ThisApplication also claims the benefit of U.S. Application No. 61/542,405filed, on Oct. 3, 2011. The disclosure of application Ser. Nos.13/633,423 and 61/542,405 are hereby incorporated by reference.

BACKGROUND OF THE INVENTION

The subject matter of the instant invention relates to a method andcomposition obtained by contacting a tertiary amine with at least oneinert gas. The tertiary amine composition can be used, for example, toproduce polyurethane foam having reduced missions.

Tertiary amines are commonly used as catalysts for the preparation ofpolyurethane materials that are widely used in consumer durable goods(such as cars, home appliances, furniture, toys, among other products)as well as in insulation of commercial and residential areas.Minimization of chemical emissions in these applications is of keyimportance to eliminate potential exposure of workers and end users tothe hazards associated by either adventitious contaminants orby-products produced by adventitious contaminants that may be present insome of the raw materials utilized in the preparation of polyurethanebased products. Controlling the presence of undesired contaminants inthe raw materials utilized to make polyurethane catalysts is an ongoingchallenge because removal of very small amount of impurities from theseraw materials is extremely difficult to achieve using conventionalseparation methods such as chromatography, distillation orrecrystallization. Most of these techniques if successfully applied willrequire extensive labor and time making these methods in many instancescost prohibited. During the preparation of polyurethane foam severalcomponents are used such as polyol, isocyanates, surfactants, blowingagents, crosslinkers, cell openers, pigments, fillers, fire retardants,metal catalysts and tertiary amine catalysts. In some cases, certaintertiary amines may contain very small amounts (ppm levels) ofcontaminants such as formaldehyde and dimethylformamide (DMF). Theconcentration of these contaminants may increase over relatively longperiods of time depending on the storage conditions.

Conventional methods for removing undesired contaminants are disclosedin the following patents. Referring now to one of those patents, U.S.Pat. No. 4,801,426 relates to a method to de-odorize malodorousaliphatic amines by flushing the amine with nitrogen gas at about 30 to100° C. to remove odorous compounds. The method is conducted on higheraliphatic amines containing long aliphatic chains in the range from C₈to C₄₀.

U.S. Pat. No. 7,879,928 discloses a process for preventing the formationof aldehydic compounds in polyether polyols, polyester polyols, orpolyurethanes by the incorporation of an effective amount of a phenolicantioxidant and an aminic antioxidant. The process relies upon theaddition of chemicals to the polyols or polyurethanes as well as aminiccompounds that can also decompose or create undesired emissions fromfinished products.

U.S. Pat. No. 7,169,268 discloses a process for providing tertiary amineproducts which are color stable and have greatly reduced tendency totake on color during their storage. The process relies on the additionof ethylene diamines to the distillation pot prior to or during thedistillation of the tertiary amine product. This process does notaddress the formation of color-free contaminants such asdimethylformamide or formaldehyde during storage. Instead, the processis limited to minimizing or reducing color bodies formation overtimethat are caused by the presence of impurities in the tertiary aminesthat can potentially be scavenged by the ethylenediamine prior or duringtheir distillation.

US2008/0269382 discloses a process for stabilizing organic materials.However, this process does not address the long term stability of apolyurethane additive such as a tertiary amine. Also, the processdepends on the addition of new chemicals to the polyurethane formulationwhich may cause additional undesired emissions.

US2009/0088489 discloses a reactive amine catalyst and in particulardiethylaminoethoxyethanol and/or diethylethanolamie in aqueous ororganic solutions for use in producing flexible polyurethane foam.However, this disclosure does not address the problem of how to preventthe formation of toxic chemicals such as dimethylformamide andformaldehyde on already existing amine catalysts.

US2011/0009512 relates to tertiary amine catalysts useful in theproduction of polyurethane foam. However, this disclosure does notaddress the issue of tertiary amine storage as well as minimization orreduction of dimethylformamide.

WO2010US62476 discloses a method to reduce the formation of DMF andformaldehyde of samples exposed to air using amine oxidation inhibitorssuch as free radical scavengers and/or antioxidants to prevent theoxidation of the amine. The disadvantage of the method is that requiresthe addition of new chemicals to the tertiary amine which may bringadditional environmental, health and safety issues to both the tertiaryamine as well as to the finished product.

The previously described patent applications, patents and otherdocuments are hereby incorporated by reference.

There is a need in this art for a tertiary amine composition havingrelatively low amounts of undesired contaminants and for a method toproduce an amine composition that is stable during storage and does notform such contaminants.

BRIEF SUMMARY OF THE INVENTION

The instant invention solves problems associated with the prior art byproviding a tertiary amine composition and process for making thecomposition wherein the amine is in equilibrium with an inert gaseousphase. Without wishing to be bound by any theory or explanation, it isbelieve that when certain tertiary amines are stored in sealedcontainers in which a liquid tertiary amine phase is in equilibrium withan inert gaseous phase, then the concentration of pollutants such asformaldehyde and dimethylformamide is substantially reduced (e.g., whenthe materials are stored over long periods of time). Thus, thisinvention provides a simple and cost effective solution to the problemof preventing formation or reducing the concentration of tracepollutants that may be present in tertiary amine polyurethane catalysts.The composition is obtained by flushing followed by bubbling an inertgas such as nitrogen and more preferentially argon to reduce theconcentration of any adventitious contaminants present in the tertiaryamine (e.g., free oxygen from air or oxygen reversibly bound to theamine which may have an effect on the long term stability and quality ofthe tertiary amine catalyst). Furthermore, when the tertiary aminecontains a compound containing at least one —NH₂ group (such as aprimary amine or hydrazine or a hydrazine derivative) also inequilibrium with an inert gas, then further DMF prevention or reductioncan take place overtime (storage) to the extent that DMF is or becomesnon-detectable when these amines are used in the manufacture of consumerdurable goods such as polyurethane foam articles.

One aspect of the invention relates to a composition obtained bycontacting at least one tertiary amine with at least one inert gaswherein the catalyst and gas are in equilibrium wherein the partialpressure of oxygen in the amine is less than under ambient conditions.

One aspect of the invention relates to a new amine composition that isobtained when inert gases such as argon or nitrogen are contacted with atertiary amine by first flushing followed by bubbling of a liquidtertiary amine with an inert gas. The resulting tertiary amine liquidproducts is allowed to equilibrate with the inert gas phase to provide astable form of the amine which can be more suitable for use in themanufacture of consumer durable goods. When the amine is produced andstored under the presence of an inert gas, then the finishedpolyurethane product is characterized by lower or non-detectableemissions of toxic compounds such as DMF or formaldehyde frompolyurethane foam.

The inventive composition comprises a liquid amine in equilibrium with agaseous phase in which the partial pressure of oxygen in the gaseousphase is less than about 160 mmHg (0.21 atm) and preferably less thanabout 110 mmHg (0.14 atm) and more preferably less than about 30 mmHg(0.04 atm). If the liquid amine phase also contains a compound having atleast on —NH₂ group from a primary amine or hydrazine, then furtherprevention or minimization of DMF can occur when the tertiary amine isin equilibrium with the inert gas.

Another aspect of the invention relates to a method of making apolyurethane comprising contacting at least one polyisocyanate with atleast one polyol in the presence of a catalytically effective amount ofthe inventive composition.

A further aspect of the invention relates to a polyurethane foam made byusing the inventive method and inventive composition.

The aspects of this invention can be used alone or in combination witheach other.

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 is a schematic of a system that can be used in one aspect of theinventive method for producing the inventive amine composition.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention relates to a method and composition obtained bycontacting at least one tertiary amine with at least one inert gas. Thetertiary amine catalyst can be in equilibrium with the inert gas. By“equilibrium” it is meant that after contacting (e.g., flushing orbubbling) an inert gas with at least one tertiary amine the partialpressure of oxygen in the amine is less than under ambient conditionsand the partial pressure of an inert gas is enhanced.

One aspect of the invention relates to a process for treating orproducing a tertiary amine catalyst that can be packed and stored inequilibrium with a gaseous phase composed of an inert gas such as anoble gas or nitrogen. The gaseous phase in equilibrium with the amineis enriched with the an inert gas with a partial pressure higher thanabout 600 mmHg (0.79 atm) and reduced or depleted in oxygen with apartial pressure lower than about 160 mm Hg (0.21 atm). In some cases,the partial pressure of the inert gas in equilibrium with the amine ishigher than about 650 mmHg (>0.85 atm) and more preferentially higherthan about 700 mmHg (>0.92 atm). The partial pressure of gas can bemeasured by utilizing sensors or by other techniques known in this art.For example, it is common practice to measure the partial pressure ofoxygen by using an electrochemical sensor. Other methods to measure theconcentration of oxygen are partial pressure sensor, Zirconia sensor andparamagnetic measurement.

The amine composition can be obtained by flushing followed by bubblingthe tertiary amine with the inert gas with or without stirring for atleast several minutes (e.g., for about 5 minutes to about 60 minutes),until the head space (gaseous volume in contact with the liquid tertiaryamine) is depleted of oxygen and the composition is allowed to reachequilibrium once the vessel containing the amine is tightly sealed undera slight positive pressure of inert gas.

Referring now to FIG. 1, FIG. 1 is a schematic of one aspect of theinventive method for obtaining the inventive amine composition. Theamine composition can be obtained by placing the liquid amine in asuitable container such as glass container, stainless steel pale or drumor any other suitable container made with a material compatible withtertiary amines. There are several possible designs for flushing andbubbling of the inert gas through the liquid amine. For example, in thecase of a small glass container (≦1.0 litter) a rubber septum can beutilized to separate the atmospheric air phase from the aminehead-space. A syringe connected to a gas source can be used to dispensethe inert gas by puncturing the rubber septum with the needle andallowing the gas to bubble throughout the liquid. The needle can also beconveniently connected to a sparging devise that allows all the gas tobe uniformly dispersed through the liquid. A second needle reaching onlythe top of the headspace serves as the outlet for gas. Inert gas canflow at a suitable rate as to allow oxygen to be removed from the liquidamine as well as the head space without over-pressurizing the container.For example, a suitable flow rate could be one in which onevolume-container of the inert gas is pass each 5 to 30 minutes. After 5to 10 volumes of inert gas pass through the system the outlet needle isremoved followed by the inlet needle. The liquid sample is then allowedto reach equilibrium. A similar procedure can also be followed with apale or a drum or any type of container. In the case of a drum, inertgas can be passed through a sparging tube as described above followed bycapping and sealing of the drum.

The inventive composition can be stored for a long period of time (e.g.,at least about 6 months) and it can be used in the manufacture ofpolyurethane foam. Further reduction of DMF can also be achieved whenthe liquid phase containing the tertiary amine in equilibrium with theinert gas also contains a compound containing at least one —NH₂functional group as in the case of primary amines or hydrazine orhydrazine derivatives.

In one aspect of the invention, the inventive catalyst (and any foamformulation and foam produced using the inventive catalyst) issubstantially free of anti-oxidants such as phenolic and aminicantioxidants. By “substantially free” of antioxidants, it is meant thatthe catalyst, foam formulation and resultant foam contain less thanabout 5 ppm and typically about <1 ppm of such antioxidants. This aspectof the invention can overcome problems associated with conventionalpractices that can be caused by the addition of such antioxidants (e.g.,emissions from a foam made with an antioxidant containing formulation).

In one aspect of the invention, the inventive catalyst (and any foamformulation and foam produced using the inventive catalyst) issubstantially free of DMF, formaldehyde, among other undesiredcontaminants. By “substantially free” it is meant that the catalyst,foam formulation and resultant foam contain less than about 10 ppm andtypically about ≦1.0 ppm of such contaminants.

One aspect of the invention relates to a method for making polyurethanefoams by using the inventive amine catalysts. Examples are given belowof TDI and MDI based polyurethane foam formulations which were used toevaluate the inventive amine catalyst in equilibrium with the inert gas.In the case of flexible molded foams, the pads were removed from theheated mold and allowed to cool down to room temperature to monitordimensional stability (shrinkage) or mechanically crushed to evaluatetheir physical and mechanical properties.

Hand Mix Evaluations

Hand mix experiments were conducted using the following procedure.Formulations were blended together for approximately 10 minutes using amechanical mixer equipped with a 7.6 cm diameter high shear mixingblade, rotating at 5000 rpm. Premixed formulations were maintained at 23C using a low temperature incubator. Mondur TD-80 (an 80/20 2,4/2,6isomer blend of toluene diisocyanate) or modified MDI was added to thepremix at the correct stoichiometric amount for the reported index ofeach foam. The mixture was blended together with Premier MillCorporation Series 2000, Model 89, and dispersed for approximately fiveseconds. The foaming mixture was transferred to an Imperial Bondware#GDR-170 paper bucket and allowed to free rise while data was recorded.

Machine Evaluations

Machine runs for the flexible molded foam were conducted on a Hi TechSure Shot MHR-50, cylinder displacement series and high-pressuremachine. Fresh premixes, consisting of the appropriate polyols, water,crosslinker, surfactants and catalysts for each formulation were chargedto the machine. Mondur TD-80 was used throughout the entire study. Allchemical temperatures were held at 23° C. via the machine's internaltemperature control units. Foam pours were made into an isothermallycontrolled, heated aluminum mold maintained at 63° C. The mold was atypical physical property tool designed with internal dimensions of 40.6cm×40.6 cm×10.2 cm. The mold has five vents, each approximately 1.5 mmin diameter, centered in each corner 10.0 cm from each edge and thegeometric center of the lid. The mold was sprayed with a solvent-basedrelease agent, prior to every pour and allowed to dry for one minutebefore pouring. The foam premix was puddle poured into the center of themold with a wet chemical charge weight capable of completely filling themold and obtaining the desired core densities reported. Minimum fillrequirements were established for each formulation evaluated. The foamarticle was demolded at 240 seconds (4 minutes) after the initial pour(detailed in next paragraph). Upon demold, the foam was placed through amechanical crusher or tested for Force-to-Crush (FTC) measurements orallow to cool down to determine dimensional stability (detailed below).Foam physical properties of each catalyst set were mechanically crushed1 minute after demold using a Black Brothers Roller crusher set to a gapof 2.54 cm. Crushing was conducted three times on each part, rotatingthe foam 90 degrees after each pass through the rollers. All partsproduced for physical testing were allowed to condition for at leastseven days in a constant temperature and humidity room (23° C., 50%relative humidity).

FTC measurements were conducted 45 seconds after demold. The pad wasremoved from the mold, weighed and placed in the FTC apparatus. Theforce detection device is equipped with a 2.2 kg capacity pressuretransducer mounted between the 323 cm2 circular plate cross head and thedrive shaft. The actual force is shown on a digital display. This devicemimics the ASTM D-3574, Indentation Force Deflection Test and provides anumerical value of freshly demolded foam's initial hardness or softness.The pad was compressed to 50 percent of its original thickness at across-head velocity of 275 mm per minute with the force necessary toachieve the highest compression cycle recorded in Newton's. Tencompression cycles were completed. A cycle takes approximately 30seconds to complete.

Preparation of Foams

Foams of any of the various types known in the art may be made using themethods of this invention, using typical polyurethane formulations. Forexample, flexible polyurethane foams with excellent physical propertiesdescribed herein will typically comprise the components shown below inTable 1, in the amounts indicated. The components shown in Table 1 willbe discussed in detail below.

TABLE 1 Polyurethane Components Component Pphp Polyol 20-100 Polymerpolyol 0-80 Natural oil polyol Varied Silicone surfactant 0.5-10 Blowing agent  2-4.5 Crosslinker 0.5-2.0  Catalyst 0.25-10   Isocyanateindex 70-115

The amount of polyisocyanate used in polyurethane formulations accordingto the invention is not limited, but it will typically be within thoseranges known to those of skill in the art. An exemplary range is givenin table 1, indicated by reference to “NCO Index” (isocyanate index). Asis known in the art, the NCO index is defined as the number ofequivalents of isocyanate, divided by the total number of equivalents ofactive hydrogen, multiplied by 100. The NCO index is represented by thefollowing formula. NCO index=[NCO/(OH+NH)]*100.

Flexible foams typically use copolymer polyols as part of the overallpolyol content in the foam composition, along with base polyols of about4000-5000 weight average molecular weight and hydroxyl number of about28-35. Base polyols and copolymer polyols will be described in detaillater herein.

Catalysts

The catalyst of the present invention comprises any tertiary amine thathas been stored and maintained in equilibrium with a gas phase rich inan inert gas (e.g., a tertiary amine produced in accordance with theinventive method). Tertiary amine catalysts can contain anisocyanate-reactive group or not. Isocyanate reactive groups compriseprimary amine, secondary amine, hydroxyl group, amide or urea. Tertiaryamine catalysts containing isocyanate reactive groups include bothgelling and blowing catalysts. Exemplary gelling catalysts include atleast one member selected from the group consisting ofN,N-bis(3-dimethylaminopropyl)-N-isopropanolamine;N,N-dimethylaminoethyl-N′-methyl ethanolamine (DABCO® T, Air Productsand Chemicals, Inc. of Allentown, Pa.); N,N,N′-trimethylaminopropylethanolamine (POLYCAT® 17, by Air Products and Chemicals, Inc.),N,N-dimethylethanolamine (DABCO® DMEA); N,N-dimethyl-N′,N′-2-hydroxy(propyl)-1,3-propylenediamine;dimethylaminopropylamine (DMAPA); (N,N-dimethylaminoethoxy)ethanol,methyl-hydroxy-ethyl-piperazine, bis(N,N-dimethyl-3-aminopropyl)amine(POLYCAT® 15), N,N-dimethylaminopropyl urea (DABCO® NE1060, DABCO®NE1070), N,N′-bis(3-dimethylaminopropyl) urea (DABCO® NE1070, DABCO®NE1080), bis(dimethylamino)-2-propanol, N-(3-aminopropyl)imidazole,N-(2-hydroxypropyl)imidazole, and N-(2-hydroxyethyl) imidazole.

Exemplary blowing catalysts containing isocyanate reactive groupsinclude at least one member selected from the group consisting of2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol,N,N-dimethylaminoethyl-N′-methyl-N′-ethanol (DABCO®-T),dimethylaminoethoxyethanol andN,N,N′-trimethyl-N′-3-aminopropyl-bis(aminoethyl) ether (DABCO® NE300).

The catalyst may also comprise tertiary amines that are highly volatileand not isocyanate-reactive. Suitable volatile gelling catalysts mayinclude, for example, at least one member selected from the groupconsisting of diazabicyclooctane (triethylenediamine), suppliedcommercially as DABCO®33-LV catalyst, tris(dimethyalminopropyl)amine(Polycat® 9), dimethylaminocyclohexylamine (Polycat® 8) andbis(dimethylaminopropyl)-N-methylamine (Polycat® 77),N,N-dimethylcyclohexylamine (Polycat-8, Air Products and Chemicals, Inc.of Allentown, Pa.), N-Methyldicyclohexylamine (Polycat-12, Air Productsand Chemicals, Inc. of Allentown, Pa.). Suitable volatile blowingcatalysts include, for example, at least one member selected from thegroup consisting of bis-dimethylaminoethyl ether, commercially suppliedas DABCO® BL-11 catalyst by Air Products and Chemicals, Inc.; as well aspentamethyldiethylenetriamine (POLYCAT® 5, Air Products and Chemicals,Inc.), hexamethyltriethylenetetramine, heptamethyltetraethylenepentamineand related compositions; higher permethylated polyamines;2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol and relatedstructures; alkoxylated polyamines; imidazole-boron compositions; oramino propyl-bis(amino-ethyl)ether compositions. The catalystcompositions may also include other components, for example transitionmetal catalysts such as organotin compounds.

Typically, the loading of non-fugitive tertiary amine catalyst(s) formaking foam according to the invention will be in the range of about 0.1to about 20 pphp, more typically about 0.1 to about 10 pphp, and mosttypically about 0.1 to about 5 pphp. However, any effective amount maybe used. The term “pphp” means parts per hundred parts polyol. Theamount of volatile amine catalyst in the foam formulation can range fromabout 0.05 to about 20 pphp.

Organic Isocyanates

Suitable organic isocyanate compounds include, but are not limited to,at least one member from the group consisting of hexamethylenediisocyanate (HDI), phenylene diisocyanate (PDI), toluene diisocyanate(TDI), and 4,4′-diphenylmethane diisocyanate (MDI). In one aspect of theinvention, 2,4-TDI, 2,6-TDI, or any mixture thereof is used to producepolyurethane foams. Other suitable isocyanate compounds are diisocyanatemixtures known commercially as “crude MDI.” One example is marketed byDow Chemical Company under the name PAPI, and contains about 60% of4,4′-diphenylmethane diisocyanate along with other isomeric andanalogous higher polyisocyanates. The isocyanate index can range fromabout 80 to about 500 depending on the type of foam formulation. Forexample, flexible foams have typically an isocyanate index of 80 to 120while rigid foams such as those typically used in appliances, laminationand spray foam application can have indexes in the range of 100 to 500depending on the application. The higher indexes are commonly used withtrimerization catalyst to produce PIR foams normally used in foamlaminates that require good fire performance.

Polyol Component

Polyurethanes are produced by the reaction of organic isocyanates withthe hydroxyl groups in a polyol, typically a mixture of polyols. Thepolyol component of the reaction mixture includes at least a main or“base” polyol. Base polyols suitable for use in the invention include,as non-limiting examples, at least one member selected from the groupconsisting of polyether polyols. Polyether polyols include poly(alkyleneoxide) polymers such as poly(ethylene oxide) and poly(propylene oxide)polymers and copolymers with terminal hydroxyl groups derived frompolyhydric compounds, including diols and triols. Examples of diols andtriols for reaction with the ethylene oxide or propylene oxide includeat least one member selected from the group consisting of ethyleneglycol, propylene glycol, 1,3-butanediol, 1,4-butanediol,1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol,pentaerythritol, glycerol, diglycerol, trimethylol propane, and similarlow molecular weight polyols. Other base polyol examples known in theart include polyhydroxy-terminated acetal resins, hydroxyl-terminatedamines and hydroxyl-terminated polyamines. Examples of these and othersuitable isocyanate-reactive materials may be found in U.S. Pat. No.4,394,491; the disclosure of which is hereby incorporated by reference.Suitable polyols also include those containing tertiary amine groupsthan can catalyze the gelling and the blowing reaction of polyurethanes,for example those described in WO 03/016373 A1, WO 01/58976 A1;WO2004/060956 A1; WO03/016372 A1; and WO03/055930 A1; the disclosure ofthe foregoing is hereby incorporated by reference. Other useful polyolsmay include polyalkylene carbonate-based polyols and polyphosphate-basedpolyols. The amount of polyether polyol can range from about 20 to about100 pphp of the foam formulation.

In one aspect of the invention, a single high molecular weight polyetherpolyol may be used as the base polyol. Alternatively, a mixture of highmolecular weight polyether polyols, for example, mixtures of di- andtri-functional materials and/or different molecular weight or differentchemical composition materials may be used. Such di- and tri-functionalmaterials include, but are not limited to at least one member selectedfrom the group consisting of polyethylene glycol, polypropylene glycol,glycerol-based polyether triols, trimethylolpropane-based polyethertriols, and other similar compounds or mixtures, provided that they areester-free. In some embodiments of the invention, at least about 50 wt %of the ester-free polyol component consists of one or more polyetherpolyols.

In addition to the base polyols described above, or instead of them,materials commonly referred to as “copolymer polyols” may be included ina polyol component for use according to the invention. Copolymer polyolsmay be used in polyurethane foams to increase the resistance of the foamto deformation, for example to improve the load-bearing properties ofthe foam. Depending upon the load-bearing requirements for thepolyurethane foam, copolymer polyols may comprise from 0 to about 80percent by weight of the total polyol content. Examples of copolymerpolyols include, but are not limited to, graft polyols and polyureamodified polyols, both of which are known in the art and arecommercially available.

Graft polyols are prepared by copolymerizing vinyl monomers, typicallystyrene and acrylonitrile, in a starting polyol. The starting polyol istypically a glycerol-initiated triol, and is typically end-capped withethylene oxide (approximately 80-85% primary hydroxyl groups). Some ofthe copolymer grafts to some of the starting polyol. The graft polyolalso contains homopolymers of styrene and acrylonitrile and unalteredstarting polyol. The styrene/acrylonitrile solids content of the graftpolyol typically ranges from about 5 wt % to about 45 wt %, but any kindof graft polyol known in the art may be used.

Polyurea modified polyols are formed by the reaction of a diamine and adiisocyanate in the presence of a starting polyol, with the productcontaining polyurea dispersion. A variant of polyurea modified polyols,also suitable for use, are polyisocyanate poly addition (PIPA) polyols,which are formed by the in situ reaction of an isocyanate and analkanolamine in a polyol.

Useful polyester polyol include those produced when a dicarboxylic acidis reacted with an excess of a diol for example adipic acid or phathalicacid or phthalic anhydride with ethylene glycol or butanediol orreacting a lactone with an excess of a diol such as caprolactone withpropylene glycol. Mannich polyols are also typically used in sprayformulations. Mannich polyols are made by the condensation of phenolswith aldehydes and amines to give polyols containing multiple hydroxylgroups (2 to 8) and tertiary amine centers. Polyester polyols cannormally be present from about 0 to about 100 pphp.

Natural Oil Polyol Component

All or a portion of the polyols useful in the preparation ofpolyurethane foam from inexpensive and renewable resources are highlydesirable to minimize the depletion of fossil fuel and othernon-sustainable resources. Natural oils consist comprise triglyceridesof saturated and unsaturated fatty acids. One natural oil polyol iscastor oil, a natural triglyceride of ricinoleic acid which is commonlyused to make polyurethane foam even though it has certain limitationssuch as low hydroxyl content. Other natural oils need to be chemicallymodified to introduce sufficient hydroxyl content to make them useful inthe production of polyurethane polymers. There are two chemicallyreactive sites that can be considered when attempting to modify naturaloil or fat into a useful polyol: 1) the unsaturated sites (doublebonds); 2) the ester functionality. Unsaturated sites present in oil orfat can be hydroxylated via epoxidation/ring opening orhydroformilation/hydrogenation. Alternatively, trans-esterification canalso be utilized to introduce OH groups in natural oil and fat. Thechemical process for the preparation of natural polyols usingepoxidation route involves a reaction mixture that requires epoxidizednatural oil, a ring opening acid catalyst and a ring opener. Epoxidizednatural oils include epoxidized plant-based oils (epoxidized vegetableoils) and epoxidized animal fats. The epoxidized natural oils may befully or partially epoxidized and these oils include at least one memberselected from the group consisting of soybean oil, corn oil, sunfloweroil, olive oil, canola oil, sesame oil, palm oil, rapeseed oil, tungoil, cotton seed oil, safflower oil, peanut oil, linseed oil andcombinations thereof. Animal fats include fish, tallow and lard. Thesenatural oils are triglycerides of fatty acids which may be saturated orunsaturated with various chain lengths from C₁₂ to C₂₄. These acids canbe: 1) saturated: lauric, myristic, palmitic, steric, arachidic andlignoceric; 2) mono-unsaturated: palmitoleic, oleic, 3)poly-unsaturated: linoleic, linolenic, arachidonic. Partially or fullyepoxidized natural oil may be prepared when reacting peroxyacid undersuitable reaction conditions. Examples of peroxyacids utilized in theepoxidation of oils have been described in WO 2006/116456 A1; thedisclosure of which is hereby incorporated by reference. Ring opening ofthe epoxidized oils with alcohols, water and other compounds having oneor multiple nucleophilic groups can be used. Depending on the reactionconditions oligomerization of the epoxidized oil can also occur. Ringopening yields natural oil polyol that can be used for the manufactureof polyurethane products. In the hydroformilation/hydrogenation process,the oil is hydroformylated in a reactor filled with a hydrogen/carbonmonoxide mixture in the presence of a suitable catalyst (typicallycobalt or rhodium) to form an aldehyde which is hydrogenated in thepresence of cobalt or nickel catalyst to form a polyol. Alternatively,polyol form natural oil and fats can be produced by trans-esterificationwith a suitable poly-hydroxyl containing substance using an alkali metalor alkali earth metal base or salt as a trans-esterification catalyst.Any natural oil or alternatively any partially hydrogenated oil can beused in the transesterification process. Examples of oils include butare not limited to at least one member selected from the groupconsisting of soybean, corn, cottonseed, peanut, castor, sunflower,canola, rapeseed, safflower, fish, seal, palm, tung, olive oil or anyblend. Any multifunctional hydroxyl compound can also be used such aslactose, maltose, raffinose, sucrose, sorbitol, xylitol, erythritol,mannitol, or any combination. The amount of natural oil polyol can rangefrom about 0 to about 40 pphp of the foam formulation.

Blowing Agents

Polyurethane foam production may be aided by the inclusion of a blowingagent to produce voids in the polyurethane matrix during polymerization.Any blowing agent known in the art may be used. Suitable blowing agentsinclude compounds with low boiling points which are vaporized during theexothermic polymerization reaction. Such blowing agents are generallyinert and therefore do not decompose or react during the polymerizationreaction. Examples of inert blowing agents include, but are not limitedto, at least one member selected from the group consisting of carbondioxide, chlorofluorocarbons, hydrogenated fluorocarbons, hydrogenatedchlorofluorocarbons, fluoroolefins, chlorofluoroolef ins,hydrofluoroolef ins, hydrochlorfluoro olefins, acetone, and low-boilinghydrocarbons such as cyclopentane, isopentane, n-pentane, and theirmixtures. Other suitable blowing agents include compounds, for examplewater, that react with isocyanate compounds to produce a gas. The amountof blowing agent is typically from about 0 (water blown) to about 80pphp. Water (blow foam by reacting with isocyanate making CO₂) can bepresent in the range from about 0 (if a BA is included) to about 60 pphp(a very low density foam) and typically from about 1.0 pphp to about 10pphp and, in some cases, from about 2.0 pphp to about 5 pphp.

Other Optional Components

A variety of other components or ingredients may be included in theformulations for making foams according to the invention. Examples ofoptional components include, but are not limited to, at least one memberselected from the group consisting of cell stabilizers, crosslinkingagents, chain extenders, pigments, fillers, flame retardants, auxiliaryurethane gelling catalysts, auxiliary urethane blowing catalysts,transition metal catalysts, and combinations of any of these. Cellstabilizers can used in an amount from about 0.1 to about 20 pphp andtypically from about 0.1 to about 10 pphp and, in some cases, from about0.1 to about 5.0 pphp. Fire retardants can be used in an amount fromabout 0 to about 20 pphp and from about 0 to about 10 pphp and fromabout 0 to about 5 pphp.

Cell stabilizers may include, for example, silicone surfactants oranionic surfactants. Examples of suitable silicone surfactants include,but are not limited to, at least one member from the group consisting ofpolyalkylsiloxanes, polyoxyalkylene polyol-modifieddimethylpolysiloxanes, alkylene glycol-modified dimethylpolysiloxanes,or any combination thereof. Suitable anionic surfactants include, butare not limited to, salts of fatty acids, salts of sulfuric acid esters,salts of phosphoric acid esters, salts of sulfonic acids, andcombinations of any of these.

Crosslinking agents include, but are not limited to, at least one memberselected from the group consisting of low-molecular weight compoundscontaining at least two moieties selected from hydroxyl groups, primaryamino groups, secondary amino groups, and other activehydrogen-containing groups which are reactive with an isocyanate group.Crosslinking agents include, for example, at least one member selectedfrom the group consisting of polyhydric alcohols (especially trihydricalcohols, such as glycerol and trimethylolpropane), polyamines, andcombinations thereof. Non-limiting examples of polyamine crosslinkingagents include diethyltoluenediamine, chlorodiaminobenzene,diethanolamine, diisopropanolamine, triethanolamine, tripropanolamine,1,6-hexanediamine, and combinations thereof. Typical diaminecrosslinking agents comprise twelve carbon atoms or fewer, more commonlyseven or fewer. The amount of crosslinking agent typically ranges fromabout 0.1 pphp to about 20 pphp

Examples of chain extenders include, but are not limited to, compoundshaving hydroxyl or amino functional group, such as glycols, amines,diols, and water. Specific non-limiting examples of chain extendersinclude at least one member selected from the group consisting ofethylene glycol, diethylene glycol, propylene glycol, dipropyleneglycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentylglycol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, ethoxylatedhydroquinone, 1,4-cyclohexanediol, N-methylethanolamine,N-methylisopropanolamine, 4-aminocyclohexanol, 1,2-diaminoethane,2,4-toluenediamine, or any mixture thereof.

Pigments may be used to color code the polyurethane foams duringmanufacture, for example to identify product grade or to concealyellowing. Pigments may include any suitable organic or inorganicpigments known in the polyurethane art. For example, organic pigments orcolorants include, but are not limited to, at least one member selectedfrom the group consisting of azo/diazo dyes, phthalocyanines,dioxazines, and carbon black. Examples of inorganic pigments include,but are not limited to, titanium dioxide, iron oxides, or chromiumoxide. The amount of any pigment typically ranges from about 0 pphp toabout 15 pphp.

Fillers may be used to increase the density and load bearing propertiesof polyurethane foams. Suitable fillers include, but are not limited to,barium sulfate or calcium carbonate. The amount of any filler typicallyranges from about 0 pphp to about 30 pphp

Flame retardants may be used to reduce the flammability of polyurethanefoams. For example, suitable flame retardants include, but are notlimited to, chlorinated phosphate esters, chlorinated paraffins, ormelamine powders.

Certain aspects of the invention are demonstrated by the followingExamples which are provided only to illustrate certain aspects of theinvention and shall not limit the scope of the claims appended hereto.

Example 1 Tertiary Amine Compositional Changes with Time when theTertiary Amine is Stored in Equilibrium with a Headspace Volume Composedof Atmospheric Air

The model tertiary N,N,N′-trimethyl-N′-3-aminopropyl-bis(aminoethyl)ether (amine-1) was selected for this study because this compound iswidely used as a blowing catalyst in many commercial applications. Thecatalyst is a blowing polyurethane catalyst commonly used in flexiblemolded and flexible slabstock applications where chemical emanation isof great concern. However, the catalyst is also employed in many otherused such as rigid, semi-rigid, spray and any other application wherewater may be used to blow the polyurethane polymer. In this example, 19ml of amine-1 was placed in a 25 ml vial and the amine liquid phase wasconditioned at 55° C. with the remaining 6 ml of the vial occupied byatmospheric air in equilibrium with the liquid amine phase. The vial wasopen after 15 days to take a sample for analysis (sample #1). The vialwas closed and reconditioned at 55° C. for an additional 15 days afterwhich a second sample was taken for analysis (sample #2). The resultsshow that large increase in the concentration of formaldehyde and DMFare observed when the liquid amine is in equilibrium with air.

TABLE 1 Formaldehyde and DMF concentrations Temperature Equilibrium TimeDMF Formaldehyde (° C.)/Sample # gas (days) (ppm) (ppm) 55/#1 Air 15 14238 55/#2 Air 30 30 340

Example 2 Tertiary Amine Compositional Changes with Time when theTertiary Amine is Stored in Equilibrium with a Headspace Volume Composedof a Nitrogen Enriched Atmosphere

Amine-1 (19 ml) was placed in a 25 ml vial and the liquid was flushedwith nitrogen for 15 minutes until the 6 ml head space (gaseous volumein contact with the liquid tertiary amine) was depleted of oxygen. Thecomposition was allowed to reach equilibrium once the vial containingthe amine was tightly sealed under a slight positive pressure ofnitrogen. The vial was open after 15 days to take a sample for analysis(sample #3). The vial was closed and reconditioned at 55° C. for anadditional 15 days after which a second sample was taken for analysis(sample #4). The result shows that some increase in the concentration offormaldehyde and DMF is still observed but the final concentration ofDMF and formaldehyde is significantly lower than in example 1 where thesample was allow to reach equilibrium under air. Thus, examples 1 and 2illustrate that oxygen plays a role in increasing the concentration ofDMF and formaldehyde because when the sample is placed under a nitrogenrich atmosphere then the final concentration of DMF and formaldehyde issubstantially smaller.

TABLE 2 Formaldehyde and DMF concentrations Temperature Equilibrium TimeDMF Formaldehyde (° C.)/Sample # gas (days) (ppm) (ppm) 55/#3 Nitrogen15 7 75 55/#4 Nitrogen 30 16 122

Example 3 Tertiary Amine Compositional Changes with Time when theTertiary Amine is Stored in Equilibrium with a Different HeadspaceVolume Composed of Atmospheric Air

Amine-1 was placed in a vial and the volume of the headspace havingatmospheric air in equilibrium with the amine phase was varied to seethe effect that a larger amount of oxygen on the headspace would have onthe concentration of DMF and formaldehyde as the sample is conditionedat 55° C. over a long period of time. The results shown in table 3illustrates that a sample in equilibrium with more air for 20 days hadmore DMF and formaldehyde than a sample conditioned for 39 days withless air (<6 ml air). This example illustrates that the amount of oxygenpresent on the headspace plays a role on the final concentration of DMFand formaldehyde in the liquid phase. A headspace composed mainly ofnitrogen or an inert gas result in little or no appreciable change inthe concentration of DMF and formaldehyde.

TABLE 3 Formaldehyde and DMF concentrations Headspace Formal-Temperature Equilibrium Time volume DMF dehyde (° C.) gas (days) (ml)(ppm) (ppm) 55 Air 0 — 10 60 55 Air 20 ~6 ml 78 708 55 Air 39 <6 ml 44554

Example 4 This Example Shows that Amine-1 has No SignificantCompositional Changes when Antioxidant (Benzenepropanoic Acid, 3,5-Bis(1,1-Dimethyl-Ethyl)-4-Hydroxy-.C7-C9 Branched Alkyl Esters) is Added tothe Amine Liquid Phase

Amine-1 (19 ml) was placed in a 25 ml vial and the volume of theheadspace was first flushed and then bubbled with either nitrogen or airdepending on the sample to create and maintain a gaseous phase inequilibrium with the amine liquid phase. The antioxidant containingsolutions were prepared by dilution method and 6 vial samples wereprepared for 6 months ageing of each sample under same condition. Allsamples were conditioned at 55° C. and one vial was removed after abouta month to analyze for DMF and HCHO. The results are shown in table 4 &5. Surprisingly, it was found that when the solution is kept inequilibrium the total concentration of formaldehyde does not show anappreciable change in concentration overtime whether there isantioxidant or not even when the sample was initially placed inequilibrium with air. The sample placed initially in equilibrium withair showed higher formaldehyde concentration than the sample inequilibrium with nitrogen. However, over a long period of time thepresence or absence of antioxidant did not have a statisticallysignificant effect on reducing the concentration of formaldehyde.Without wishing to be bound by any theory or explanation, it is believedthat oxidation does eventually takes place or the formation of anamine-oxygen species is too fast for an antioxidant to compete since itsconcentration ought to be small. Thus, an effective way to prevent theformation of formaldehyde is by flushing and then bubbling nitrogen overa period of time sufficient to remove all forms of O₂ from the system.Most surprisingly was the finding that the concentration of DMF actuallydecreases with time even when the sample was initially conditioned withair and that the presence of antioxidant had no effect on thisreduction. A similar case (Table 6) is observed with other antioxidantssuch as octadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionate andvitamin E.

TABLE 4 DMF concentrations DMF Benzenepropanoic acid, 3,5-bis Anti -(1,1-dimethyl-ethyl)-4-hydroxy- oxidant ppm .C7-C9 branched alkyl estersTemp ° C. 55 Time Day 0 16 44 72 100 135 170 N₂ 5,000 3.5 2.0 1.7 1.21.0 1.0 #### 1,000 1.9 1.8 1.0 1.0 1.0 #### 500 1.5 1.0 1.0 1.0 1.1 1.00 3.8 1.6 1.0 1.0 1.0 1.0 Air 1,000 3.5 2.5 1.2 1.0 1.0 1.2 1.0 0 6.61.8 1.1 1.0 1.2 1.0

TABLE 5 Formaldehyde concentrations HCHO Benzenepropanoic acid, 3,5-bis(1,1- Anti- dimethyl-ethyl)-4-hydroxy-.C7-C9 oxidant ppm branched alkylesters Temp ° C. 55 Time Day 0 16 44 72 100 135 170 N₂ 5,000 62 57 69 7174 80 84 1,000 59 73 75 78 80 85 500 61 80 72 72 77 78 0 57 72 72 76 7375 Air 1,000 62 107 119 118 99 114 113 0 97 112 104 107 108 100

TABLE 6 DMF concentrations when using octadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionate and Vitamin E DMF Anti-octadecyl-3-(3,5-di-tert.butyl-4- oxidant ppm hydroxyphenyl)-propionateVitamin E Temp ° C. 55 RT (~25) Time Day 0 16 44 72 100 135 170 0 16 4472 100 135 170 N₂ 5,000 3.5 1.0 1.0 1.0 1.0 1.0 1.0 3.5 1.4 1.0 1.0 1.01.0 1.0 1,000 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 500 1.81.0 1.5 2.7 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 N₂ 0 3.5 3.8 1.6 1.0 1.0 1.01.0 3.5 3.8 1.6 1.0 1.0 1.0 1.0

Example 5 Argon Gas in Equilibrium with Tertiary Amine is More Efficientat Preventing Compositional Changes than Nitrogen

Argon is utilized in a similar manner as nitrogen and samples of amine-1are flushed and bubbled with argon gas until equilibrium is obtainedbetween gaseous phase and the amine liquid phase. In a 25 ml vial, 19 mlof amine-1 is placed in a 25 ml vial and the amine liquid phase isconditioned at 55° C. with the remaining 6 ml of the vial occupied byargon gas in equilibrium with the liquid amine phase. The vial is openafter 15 days to take a sample for analysis (sample #1). The vial isclosed and reconditioned at 55° C. for an additional 15 days after whicha second sample is taken for analysis (sample #2). The net result isthat smaller amount of formaldehyde and DMF is observed when the liquidsample is in equilibrium with argon relative. Thus argon is moreeffective than nitrogen at preventing the formation of formaldehyde andDMF.

Example 6 Argon Gas in Equilibrium with Tertiary Amine and in thePresence of a —NH₂ Containing Molecule to Minimize DMF and FormaldehydeFormation

Tertiary amines is flushed and bubbled with argon gas until equilibriumis obtained between gaseous phase and the amine liquid phase. Thetertiary amine in this case contains a substance that contains at leastone —NH₂ functionality such as a primary amine, hydrazine or a hydrazinederivative. In 25 ml vial, 19 ml of amine-1 is placed in a 25 ml vialand the amine liquid phase is conditioned at 55° C. with the remaining 6ml of the vial occupied by argon gas in equilibrium with the liquidamine phase. The vial is open after 15 days to take a sample foranalysis (sample #1). The vial is closed and reconditioned at 55° C. foran additional 15 days after which a second sample is taken for analysis(sample #2). The net result is that further reduction in formaldehydeand DMF is observed when the tertiary amine in equilibrium with argoncontains a —NH₂ containing substance.

Example 7 Tertiary Amine Compositional Changes with Time when theTertiary Amine is Stored in Equilibrium with a Headspace Volume Composedof Argon

In this example, 19 ml of amine-1 was placed in four different 25 mlvials and the amine liquid phase was conditioned at ambient temperature(25° C.) with the remaining 6 ml of the vial occupied by eitheratmospheric air (samples 1 and 2) or argon (samples 3 and 4) inequilibrium with the liquid amine phase. The vial was open after 30 daysto perform the analysis for DMF content. The initial content of DMF inthe sample was 7 ppm. The results shown in Table 7 illustrates that theincrease in DMF concentration was significantly reduced when the aminewas conditioned with Argon gas.

TABLE 7 DMF concentrations Temperature Equilibrium Time DMF (°C.)/Sample # Gas (days) (ppm) 25/Initial Air 0 7 25/#1 Air 30 27 25/#2Air 30 22 25/#3 Argon 30 9 25/#4 Argon 30 10

Example 8 This Example Shows that Amine-1 can be Used as a BlowingCatalyst to Make Polyurethane Foam with a Wide Variety of GellingPolyurethane Foam Catalyst

Foam pads were prepared by adding a tertiary amine catalyst to about 302g of a premix (prepared as in Table 8) in a 32 oz (951 ml) paper cup.The formulation was mixed for about 10 seconds at about 6,000 RPM usingan overhead stirrer fitted with a 2-inch (5.1 cm) diameter stirringpaddle.

The toluene diisocyanate was then added, and the formulation was mixedwell for about another 6 seconds at about 6,000 RPM using the samestirrer, after which it was poured into a pre-heated mold at 70° C. anddemolded after 4 minutes. The foam pads were removed from the mold, handcrushed, weighed and machine crushed at 75% pad thickness. Foam padswere stored under constant temperature and humidity conditions for 48hours before being cut and tested.

TABLE 8 PREMIX COMPONENTS #1 Component PPHP SPECFLEX ® NC 630¹ 50SPECFLEX ® NC 700² 50 Water 3.0 DABCO ® DC6070³ 0.60 Catalyst VariedDiethanolamine (crosslinker) 0.70 Toluene diisocyanate To provide NCOindex = 100 ¹High functionality capped polyether polyol of highmolecular weight, functionality, and primary hydroxyl content with abase polyol molecular weight of about 5500, available from Dow ChemicalCompany, Midland, MI ²Grafted polyether polyol containing copolymerizedstyrene and acrylonitrile, base polyol molecular weight about 4800,available from Dow Chemical Company, Midland, MI ³Silicone surfactant isavailable from Air Products and Chemicals, Inc. ⁴ The amine catalyst isavailable from Air Products and Chemicals, Inc.

The toluene diisocyanate was then added, and the formulation was mixedwell for about another 6 seconds at about 6,000 RPM using the samestirrer, after which it was poured into a pre-heated mold at 70° C. anddemolded after 4 minutes. The foam pads were removed from the mold, handcrushed, weighed and machine crushed at 75% pad thickness. Dimensionalstability (foam shrinkage) was evaluated by allowing the foam pads tocool down and observing whether shrinkage or not took place. Foam padswere stored under constant temperature and humidity conditions for 48hours before being cut and tested.

Table 9 shows physical properties of flexible molded polyurethane foampads for gelling catalysts with different molecular structures andisocyanate reactive functionalities. The flexible molded pads were madeusing a single gelling amine catalyst to show the influence of eachindividual structure on physical properties. The blowing catalyst was ineach case was amine-1 (N,N,N′-trimethyl-N′-3-aminopropyl-bis(aminoethyl)ether).

TABLE 9 PHYSICAL PROPERTIES AT AMBIENT DATA 50% CS Tear TensileElongation Airflow Height Density Catalyst (lbf) (psi) (%) (SCFM) Loss(lb/cuft) Triethylenediamine (1) 1.63 17.4 99.3 2.31 8.21 1.89Bis(dimethylaminopropyl) 1.27 14.3 82.1 1.94 11.86 1.95 amine (2)Dimethylaminoethoxyethanol 1.40 15.3 151.7 1.74 6.18 1.87 (3)Dimethylaminopropylureas 1.26 15.0 158.9 2.12 4.96 1.84 (mono and bismixture) (4) N,N-bis(dimethylamino 1.54 15.7 155.8 1.78 4.83 1.86propyl)-N-(2- hydroypropyl)amine (5) N-dimethylaminopropyl-N-(2- 1.3716.3 94.4 2.11 40.9 1.81 hydroxyethyl)-N- methylamine (6)N-dimethylaminoethyl-N-(2- 1.55 17.0 105.8 2.02 43.7 1.80hydroxyethyl)-N- methylamine (7)

While the invention has been described with reference to certain aspectsor embodiments, it will be understood by those skilled in the art thatvarious changes may be made and equivalents may be substituted forelements thereof without departing from the scope of the invention. Inaddition, many modifications may be made to adapt a particular situationor material to the teachings of the invention without departing from theessential scope thereof including usage of these aspects alone or incombination with each other. Therefore, it is intended that theinvention not be limited to the particular embodiment disclosed, forexample, as the best mode contemplated for carrying out this invention,but that the invention will include all aspects or embodiments fallingwithin the scope of the appended claims.

1-10. (canceled)
 11. A method of making a polyurethane comprisingcontacting at least one polyisocyanate with at least one polyol in thepresence of a catalytically effective amount of a composition obtainedby contacting at least one tertiary amine with at least one inert gaswherein the catalyst and gas are in equilibrium wherein the partialpressure of oxygen in the amine is less than under ambient conditions.12. The method of claim 11, wherein the contacting of the at least onepolyisocyanate and the polyol occurs in the presence of at least oneblowing agent under conditions sufficient to produce a polyurethanefoam.
 13. The method of claim 11 wherein the composition is obtained bycontacting at least one liquid tertiary amine with at least one inertgas wherein the amine and gas are in equilibrium and wherein the partialpressure of oxygen in the composition is less than under ambientconditions and wherein the amine contains at least one isocyanatereactive group comprising at least one member selected from the groupconsisting of secondary amine, hydroxyl, amide and urea and thecomposition is substantially free of anti-oxidants, DMF andformaldehyde.
 14. The method of claim 11 wherein the inert gas comprisesat least one of nitrogen and argon.
 15. The method of claim 14 whereinthe inert gas comprises argon.
 16. The method of claim 11 wherein thecomposition is substantially free of DMF and formaldehyde.
 17. Themethod of claim 11 wherein the contacting of the at least onepolyisocyanate and the polyol occurs in the presence of water, at leastone crosslinker, and at least one silicone surfactant.
 18. The method ofclaim 11 wherein at least one tertiary amine comprisesN,N,N′-trimethyl-N′-3-aminopropyl-bis(aminoethyl) ether.
 19. The methodof claim 11 wherein the at least one tertiary amine comprises a blowingcatalyst.
 20. The method of claim 19 further comprising at least onemember selected from the group consisting of triethylenediamine,bis(dimethylaminopropyl) amine, dimethylaminoethoxyethanol,dimethylaminopropylureas, N,N-bis(dimethylaminopropyl)-N-(2-hydroypropyl)amine,N-dimethylaminopropyl-N-(2-hydroxyethyl)-N-methylamine, andN-dimethylaminoethyl-N-(2-hydroxyethyl)-N-methylamine.
 21. The method ofclaim 11 wherein the composition comprises at least one liquid tertiaryamine catalyst that has been bubbled with at least one inert gas whereinthe amine catalyst and gas are in equilibrium and wherein the partialpressure of oxygen in the amine catalyst in the container is less thanunder ambient conditions and wherein the composition is substantiallyfree of anti-oxidants, DMF and formaldehyde.
 22. The method of claim 11wherein the composition is obtained by contacting at least one liquidtertiary amine catalyst with at least one inert gas wherein the aminecatalyst and gas are in equilibrium; wherein the composition issubstantially free of anti-oxidants and wherein the partial pressure ofinert gas is higher than about 600 mmHg (0.79 atm) and the partialpressure of oxygen is lower than about 160 mm Hg (0.21 atm).
 23. Themethod of claim 11 wherein the tertiary amine catalyst contains at leastone isocyanate-reactive group comprising at least one member consistingof primary amine, secondary amine, hydroxyl group, amide and urea. 24.The method of claim 11 wherein the tertiary amine catalyst comprises atleast one member selected from the group consisting ofN,N-bis(3-dimethylaminopropyl)-N-isopropanolamine;N,N-dimethylaminoethyl-N′-methyl ethanolamine;N,N,N′-trimethylaminopropyl ethanolamine, N,N-dimethylethanolamine;N,N-dimethyl-N′,N′-2-hydroxy(propyl)-1,3-propylenediamine;dimethylaminopropylamine; (N,N-dimethylaminoethoxy)ethanol,methyl-hydroxy-ethyl-piperazine, bis(N,N-dimethyl-3-aminopropyl)amine,N,N-dimethylaminopropyl urea, N,N′-bis(3-dimethylaminopropyl) urea,bis(dimethylamino)-2-propanol, N-(3-aminopropyl)imidazole,N-(2-hydroxypropyl)imidazole, and N-(2-hydroxyethyl) imidazole.
 25. Themethod of claim 11 wherein the tertiary amine catalyst comprises atleast one member selected from the group consisting of2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol,N,N-dimethylaminoethyl-N′-methyl-N′-ethanol, dimethylaminoethoxyethanoland N,N,N′-trimethyl-N′-3-aminopropyl-bis(aminoethyl) ether.
 26. Themethod of claim 11 wherein the tertiary amine catalyst comprises atleast one member selected from the group consisting ofdiazabicyclooctane, tris(dimethyalminopropyl)amine,dimethylaminocyclohexylamine, bis(dimethylaminopropyl)-N-methylamine,N,N-dimethylcyclohexylamine, and N-Methyldicyclohexylamine.
 27. Themethod of claim 11 wherein the tertiary amine catalyst comprises atleast one member selected from the group consisting ofbis-dimethylaminoethyl ether, pentamethyldiethylenetriamine,hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine,2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol, alkoxylatedpolyamines; imidazole-boron compositions; and aminopropyl-bis(amino-ethyl)ether compositions.
 28. The method of claim 11wherein the method further comprising molding a contact product ofpolyol and polyisocyanate.
 29. An article of manufacture comprising thepolyurethane foam prepared by the method of claim 12.